Electrolytic manganese cell



M. c. CAROSELLA 2,739,116

ELECTROLYTIC MANGANESE CELL March 20, 1956 2 Sheets-Sheet l Filed March 5, 1953 5 1 INVENTORI MICHAEL C. CAROSELLA ATTORNEY March 1955 M. c. CAROSELLA ELECTROLYTIC MANGANESE CELL 2 Sheets-Sheet 2 Filed March 5, 1953 g 1 A H. 0 A ll 2 Z 6 4 1 1 2 a 6 3% ENE- r $A\ W\* h A "M M v 9 9 w I I L wAl I31 9A 4 m 2 H3 1 ,2 "P 5 H 7 m m I 4 M. M m L I F w (2 v a mm m a my "7 INVENTOR MICHAEL C. CAROSELLA BY 2 i i ATTORNEY Uni e s te Patent-"O 2,139,116 ELECTROLYTIC MANGANESE CELL Michael Cr Carosella, Niagara Falls, N. 'Y., assignor to Union Carbide and Carbon Corporation, incorporation of New York I Application March 5, 1953, Serial No. 340,555

2 Claims. .(Ci. 1204-2571) The present invention relates to cells for the electrowinning of manganese and, more particularly, to such cells of the compartment type.

Hereto ore, many cell constructions have been proposed but none has satisfactorily simplifiedthe problems otanodic sludge removal and .cell feed. U; S. Patent No. 2,603,594 to F. W. Woodman et a1. discloses a cell having a common catholyte feed, thereby simplifying the problem of supplyingcatholyte to each of the catholyte compartments. Such common catholyte feed provides a means for easily controlling the pH and manganese concentration of the individual catholyte solutions. The cell of that patent, "however, is subject to the disadvantage that no means is providedfor removal o'fanodic M1102 sludge as it builds up in the anode compartments. Periodic shutdown is required to remove this buildup which would result in the bursting of the diaphragm bagsif allowed to continue] Anattempt to solve theprobi'em of anodic sludge buildup was disclosed in S. Patent No. 2,456,196 to L H. llacobs et ad. by providinga cell having a false bottom compartment "into "which the anodic sludge passesas it builds up in the plurality of anode compartments. Although this cell presents a solution to the problem of anodic sludge buildup, it is disadvantageous in that it requires that'the false bottom be periodically actually torn out to clean the sludge irorn the false bottom compartment. Such a periodic procedure is both time consuming and costly. Additionally, should a :leak develop through any of .the many diaphragms or in the false bottom, an intermixing olrcathol'ytc andano'lyte will occur and (the ventire'cell wouldhave to be disassembled for repair. i

It is, accordingly, an object of the present invention to provide an electrowinning .cell having means for efiiciently removing anodic sludge from the anode compartments to such locations where it can easily be removed.

A further object is to provide an electrowinning cell which, while providing for the easy removal of anodic sludge, reduces the chances of intermiXture of anolyte and catholyte solutions.

A still further object is to provide a cell wherein a ruptured diaphragm can be replaced without disassembling the entire cell.

In the drawings:

Fig. 1 is a vertical front sectional view of an electrowinning cell embodying the present invention, with parts broken away and in section;

Fig. 2 is an end sectional view of the cell along the line 2-2 of Fig. 1; and

Fig. 3 is an enlarged partial plan sectional view of the cell taken approximately along the line 3-3 of Fig. 1, with parts broken away and in section.

As shown in the drawings, the cell 1 of the present invention comprises a box-like shell having side frames 2 of wood or other suitable material, bottom frames 3, a cell support 4 and a suitable lining S of a suitable metal, or other resistant material. The vertical partition 6 divides the interior of cell 1 into two compartments 7 and ice .8. The relatively large compartment 8 has positioned at its base a compartment-supporting frame 9 which supports the cathode compartments. The diaphragm 10 divide the upper portion of large compartment .8 into a plurality of individual catholyte compartments 11 which are separated from each other so as to provide spaces 12 for the insertion of anodes therebet-ween. Each of the catholyte compartments communicates, through vertical partition 6, with compartment 7 which serves as a common catholyte feed compartment. This communication is established through the plurality of conduits 13 and 14 which supply catholyte .feed to and remove spent catholyte from each of the plurality of catholyte compartments.

The plurality of individual catholyte compartments are closed compartments communicating with the rest of compartment 8 only through the plurality of diaphragms. The plurality of anode spaces 12 formed between the individual catholyte compartments freely communicate at their sides and bottom with the rest of the anolyte compartment 3. Therefore, the major portion of large compartment 8 operates as a common anolyte compart ment communicating with each of the plurality of individual anode spaces between the individual catholyte compartments. In this manner any anodic sludge formed at the plurality of individual anodes can freely pass to the bottom of the compartment 8 where it can easily be removed through the ano'lyte drain described below.

partments is suspended, in sheet form, a metallic cathode 15 of stainless steel, or some other suitable material, held in aholder 16.

In each of the plurality of individual anode spaces 12 is suspended a metallic anode composed of 99% lead- 'l% silver alloy, or some other suitable material. These anodes may be of any suitable shape, such as the rod form which is shown in the drawings. As there shown, each anode comprises a plurality of cylindrical rods 17 which are assembled and held in supporting means to form an integral anode assembly 18. The .use of such anodes in the .electrowinning of manganese .is disclosed in greater detail in my copending application Serial No. 340,556., filed concurrently with this application.

In the embodiment shown in .the drawing, the cell .is provided with a feeding trough 19 through which fresh electrolyte passes into the .cell. This cell feed then passes through ports 20 into the common catholyte'feed compartment 7. A catholyte overflow port 21 is also provided to maintain the catholyte level at a desired level and provide for circulation of the catholyte solution if desired.

Anolyte overflow means 22 is also provided to allow removal of spent anolyte from the anolyte compartment. This is accomplished by removing the overflow anolyte from the bottom of the anolyte compartment through the vertical conduit 23 which communicates between the bottom of the anolyte compartment 8 and overflow means 22.

When it is desirable to remove the anolyte (or anodic sludge) and catholyte from the cell this may be accomplished through the use of the anolyte drain 24 and the catholyte drain 25 which are positioned at the base of the cell.

In operation for a complete cycle, cell feed is supplied to the cell 1 through feeding trough 19 where it passes through ports 20 into the catholyte feed compartment 7. Circulation of catholyte is established between the catholyte feed compartment and the individual catholyte compartments through the plurality of inlet ports 13 and outlet ports 14. As electrowinning takes place catholyte is depleted in manganese in the cathode compartments 11 and flows through the diaphragms 10 to the anode spaces 12 of the anolyte compartment 8. Anolyte circulates between the plurality of anode spaces 12 and the rest of compartment 8 with the exception of that portion of compartment 8 which is taken up by the plurality of individual catholyte compartments 11. Anolyte is removed from the system through vertical compartment 23 and anolyte overflow means 22 in amounts equivalent to the cell feed which is constantly added to the cell.

It has been found that the cell, as described above and shown in the drawings, has provided a simple solution to the problem of anodic sludge removal while at the same time providing a simple means for controlling the pH and manganese concentration of the catholyte solution. The former is readily accomplished through providing a large compartment below the plurality of anodes, While the latter is accomplished through providing a common catholyte feed compartment wherein the pH and manganese content of all cell feed solutions can be simply adjusted as a single solution.

The following is an example of the operation of a cell embodying the present invention:

(I A n Anode u 5) rods 5 diam. x 38%.

o anodes per cell.

Stainless steel. (,alihodo X 22 X ,1

-l cathodes per cell. Current density, anodo [2-19 amp. per sq. ft. Current density, cathode." amp. per sq. ft. (.011 voltage 5.5 volts.

Mn: 34-36 grams per liter. (NH;)2SO4I125145 grams per lit S0 more than 0.10 gram per liter.

l Ill 10 to 12 grams per liter.

(XHU SO, 115-165 grams per liter (calculated from ammonia Food solution Cath olyte content). 2111011: than 0.1.0 grain per liter. Mu 2010 to 2 grams per liter. H 8 4 39- 6 "rams per i er. Awlym (l\'lI i SO4:1231-l5 grams per iter. Diaphragm] 18-02:. canvas. Duration of electrolysis- 48 hours. Pounds of Mn per catl10de 31. Current eiiiciency It is to be understood that the present invention also includes an arrangement wherein the common catholyte feed compartment is positioned separate and apart from the rest of the box-like cell and communicates with the plurality of individual catholyte compartments by means of catholyte feed tubes.

What is claimed is:

1. An electrolytic cell for the electrowinning of manganese comprising a box having an internal vertical partition dividing the interior thereof into a common catholyte feed compartment and an electrolyte compartment; means for introducing cell feed to said common catholyte compartment; a plurality of anode and cathode plates suspended in said electrolyte compartment; frames carrying solution permeable diaphragms spaced from opposite sides of and surrounding each of said cathode plates to form individual catholyte compartments, individual anode spaces alternately positioned therebetween, and a common anolyte compartment surrounding said individual catholyte compartments and communicating with each of said individual anode spaces at the sides and bottoms thereof; and conduit means communicating between said common catholyte feed compartment and each of said individual catholyte compartments for supplying catholyte feed thereto.

2. An electrolytic cell for the electrowinning of manganese comprising a box having an internal vertical partition dividing the interior thereof into a common catholyte feed compartment and an electrolyte compartment; means for introducing cell feed to said common catholyte compartment; a plurality of anode and cathode plates suspended in said electrolyte compartment; frames carrying solution permeable diaphragms spaced from opposite sides of and surrounding each of said cathode plates to form individual catholyte compartments, individual anode spaces alternately positioned therebetween, and a common anolyte compartment surrounding said individual catholyte compartments and communicating with each of said individual anode spaces at the sides and bottoms thereof; conduit means communicating between said common catholyte feed compartment and each of said individual catholyte compartments for supplying catholyte feed thereto, conduit means connected to said common anolyte compartment for removing anolyte therefrom as cell feed solution is supplied to the cell; and discharge means at the base of said common anolyte compartment for removing anodic sludge therefrom.

Bureau of Mines Bulletin 463 (1946), pages 63, 64 and 65.

Lloyd et al.: Abstract of Application 238, 361, published Oct. 14, 1952. 

1. AN ELECTROLYTIC CELL FOR THE ELECTROWINNING OF MANGANESE COMPRISING A BOX HAVING AN INTERNAL VERTICAL PARTITION DIVIDING THE INTERIOR THEREOF INTO A COMMON CATHOLYTE FEED COMPARTMENT AND AN ELECTROLYTE COMPARTMENT; MEANS FOR INTRODUCING CELL FEED TO SAID COMMON CATHOLYTE COMPARTMENT; A PLURALITY OF ANODE AND CATHODE PLATES SUSPENDED IN SAID ELECTROLYTE COMPARTMENT; FRAMES CARRYING SOLUTION PERMEABLE DIAPHRAGMS SPACED FROM OPPOSITE SIDES OF AND SURROUNDING EACH OF SAID CATHODE PLATES TO FORM INDIVIDUAL CATHOLYTE COMPARTMENTS, INDIVIDUAL ANODE SPACES ALTERNATELY POSITIONED THEREBETWEEN, AND A COMMON ANOLYTE COMPARTMENT SURROUNDING SAID INDIVIDUAL CATHOLYTE COMPARTMENTS AND COMMUNICATING WITH EACH OF SAID INDIVIDUAL ANODE SPACES AT THE SIDES AND BOTTOMS THEREOF; AND CONDUIT MEANS COMMUNICATING BETWEEN SAID COMMON CATHOLYTE FEED COMPARTMENT AND EACH OF SAID INDIVIDUAL CATHOLYTE COMPARTMENTS FOR SUPPLYING CATHOLYTE FEED THERETO. 